高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (12): 2191-2198.doi: 10.7503/cjcu20160487

• 物理化学 • 上一篇    下一篇

H2O2/[CnMIm]HCO3对CEES的消毒动力学及机理

王志成1, 习海玲1,2(), 孔令策1, 赵三平1, 左言军1   

  1. 1. 防化研究院, 2. 国民核生化灾害防护国家重点实验室, 北京 102205
  • 收稿日期:2016-07-08 出版日期:2016-12-10 发布日期:2016-11-18
  • 作者简介:联系人简介: 习海玲, 女, 研究员, 博士生导师, 主要从事军事化学方面的研究. E-mail:fhxihl@163.com
  • 基金资助:
    国民核化生灾害防护国家重点实验室项目(批准号: SKLNBC2012-09)资助

Kinetics and Mechanism of Decontamination Reaction of CEES in H2O2/[CnMIm]HCO3

WANG Zhicheng1, XI Hailing1,2,*(), KONG Lingce1, ZHAO Sanping2, ZUO Yanjun1   

  1. 1. Research Institute of Chemical Defence, 2. State Key Laboratory of Civil Nuclear,Biological, and Chemical Defence, Beijing 102205, China
  • Received:2016-07-08 Online:2016-12-10 Published:2016-11-18
  • Contact: XI Hailing E-mail:fhxihl@163.com

摘要:

合成了4种不同烷基链长的1-烷基-3-甲基咪唑碳酸氢盐([CnMIm]HCO3, n=2, 4, 6, 8)离子液体(ILs), 并以H2O2水溶液(质量分数30%)为氧化剂, 研究了H2O2在[CnMIm]HCO3离子液体、 H2O和C2H5OH中对芥子气模拟剂2-氯乙基乙基硫醚(CEES)的消毒能力, 考察了离子液体烷基链长、 H2O2/CEES摩尔比和反应温度对消毒率的影响, 并对反应活化能和产物进行了分析. 结果表明, H2O2在不同溶剂中对CEES的消毒能力依次为[BMIm]HCO3>[EMIm]HCO3>[HMIm]HCO3>[OMIm]HCO3>C2H5OH>H2O. 对于CEES在[BMIm]HCO3中形成的20 mg/mL的毒剂溶液, 当n(H2O2)∶n(CEES)=10时, H2O2可在30 min内消毒99.58%的CEES, 且该体系具有一定的低温(243 K)消毒能力. 该反应为一级反应, 活化能为15.59 kJ/mol, 低于单一过碳酸钠与CEES的反应活化能. 化学发光测试结果表明, 在碳酸氢根活化过氧化氢(BAP)体系中, 咪唑基离子液体可抑制亚砜被超氧阴离子(·O-2)过度氧化为砜.

关键词: 离子液体, 洗消, 2-氯乙基乙基硫醚, 碳酸氢根活化过氧化氢

Abstract:

A series of environmentally benign 1-n-alkyl-3-methylimidazolium bicarbonate ionic liquids(ILs)([CnMIm]HCO3, n=2, 4, 6, 8) was synthesized and hydrogen peroxide was employed in decontamination against 2-chloroethyl ethyl sulfide(CEES, a mustard agent simulant) in these ILs. The influencing factors such as ILs alkyl chain length, oxidant/CEES molar ratio and temperature were tested and the activation energy, reaction product in H2O2/[BMIm]HCO3 was analyzed. The results indicated that the solvents species can affect decontamination efficacy against CEES and they were in the following sequences: [BMIm]HCO3>[EMIm]HCO3>[HMIm]HCO3>[OMIm]HCO3>C2H5OH> H2O. In H2O2/[BMIm]HCO3 system, 99.58% of the CEES was oxidized mainly to corresponding sulfoxide after 30 min at the concentration of 20 mg/mL and O/S molar ratio of 10. The apparent activation energy of CEES oxidized by H2O2/[BMIm]HCO3 was 15.59 kJ/mol. Moreover, the superoxide radical anion(·O-2) could be produced and oxidized ILs to 2-imidazolone, which inhibited the formation of corrosive sulfone. The result indicated that H2O2/[BMIm]HCO3 system may be a new option for decontamination against CEES.

Key words: Ionic liquid, Decontamination, 2-Chloroethyl ethyl sulfide, Bicarbonate activation of H2O2

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